Organometallics
Article
128.51 (C5′′), 127.72 (C7′), 116.20 (C5′), 114.67 (C8′), 114.47
(C3), 113.10 (C5), 109.69 (C4′′), 49.28 (C1′′′), 22.54 (C2′′′), 11.25
(C3′′′) ppm; 19F NMR (376 MHz, DMSO-d6) δ −77.75 ppm; HRMS
(ESI) m/z calcd for C19H18N54SO3F3 [M − CF3SO3]+ 304.1557,
found 304.1563.
ppm; HRMS (MALDI): m/z calcd for C18H17ClN5PF6Pd [M − PF6]+
446.0205, found 446.0209.
Palladium Complex 6f.
General Procedure for Synthesis of Palladium Complexes.
The benzimidazolium salt (0.5 mmol) and Ag2O (0.38 mmol, 87 mg)
were successively placed in a 25 mL flask and dissolved in MeCN (2
mL). The mixtures were subsequently stirred at room temperature in
the dark for 8 h. Without a purification step, Pd(CH3CN)2Cl2 (1.0
mmol, 260 mg) was added to the reaction mixture, which was
continuously stirred at room temperature for 8 h. The reaction mixture
was added to brine (15 mL) and extracted three times with
dichloromethane (3 × 15 mL). The solvent was concentrated under
vacuum, and the palladium complexes were isolated by flash
chromatography.
Purification by flash chromatography (DCM/MeOH = 10/1): a pale
yellow solid (173 mg, 65%), mp 234.5−235.6 °C; H NMR (400
1
MHz, DMSO-d6) δ 9.23 (d, J = 2.8 Hz, 1H, 5′′-H), 8.66 (t, J = 8.0 Hz,
1H, 5′-H), 8.41 (t, J = 8.0 Hz, 2H, 4-H and 8′-H), 8.19 (d, J = 8.4 Hz,
1H, 5-H), 8.04−8.00 (m, 2H, 3-H and 3′′-H), 7.70−7.62 (m, 2H, 6′-H
and 7′-H), 6.97 (t, J = 2.4 Hz, 1H, 4′′-H), 4.67 (t, J = 8.0 Hz, 2H, 1′′′-
H), 1.87−1.79 (m, 2H, 2′′′-H), 0.92 (t, J = 7.6 Hz, 3H, 3′′′-H) ppm;
13C NMR (100 MHz, DMSO-d6) δ 162.59 (Pd−C), 149.16 (C2),
147.97 (C6), 147.29 (C4), 144.97 (C3′′), 133.93 (C4′), 132.97 (C9′),
129.74 (C6′), 127.55 (C5′′), 126.85 (C7′), 114.07 (C5′), 113.43
(C8′), 111.55 (C3), 110.71 (C5), 109.27 (C4′′), 49.14 (C1′′′), 23.42
(C2′′′), 11.0 (C3′′′) ppm; 19F NMR (376 MHz, DMSO-d6) δ
−148.26 ppm; HRMS (MALDI): m/z calcd for C18H17ClBF4N5Pd [M
− BF4]+ 446.0205, found 446.0193.
Palladium Complex 3.
Purification by flash chromatography (DCM/MeOH = 30/1): a
yellow solid (142 mg, 57%), mp 185.2−186.1 °C; A mixture of two
Palladium Complex 6g.
1
rotamers (3a:3b = 1.4/1); H NMR (400 MHz, CDCl3) δ 10.91 (s,
1H, NH-3a-H), 10.71 (s, 1H, NH-3b-H), 8.23−8.18 (m, 2H3a and
2H3b 5′′, 6′-3a-H and 5′′, 6′-3b-H), 8.19 (s, 1H, CHO-3a-H), 8.14 (s,
1H, CHO-3b-H), 7.59 (t, J = 8.0 Hz, 1H, 3′′-3a-H), 7.54 (t, J = 8.0
Hz, 1H, 3′′-3b-H), 7.47−7.27 (m, 4H3a and 4H3b 4,5,5′,3′-3a-H and
4,5,5′,3′-3b-H), 6.83 (d, J = 7.6 Hz, 1H, 4′-3a-H), 6.78 (d, J = 7.6 Hz,
1H, 4′-3b-H), 6.70 (t, J = 2.8 Hz, 1H, 3-3a-H), 6.68 (t, J = 2.4 Hz, 1H,
3-3b-H), 6.48 (d, J = 8.8 Hz, 1H, 4′′-3b-H), 6.14 (d, J = 8.4 Hz, 1H,
4′′-3a-H), 3.71 (t, J = 7.6 Hz, 2H, 1′′′-3a-H), 3.63 (t, J = 7.6 Hz, 2H,
1′′′-3b-H), 1.63−1.57 (m, 2H, 2′′′-3b-H), 1.55−1.47 (m, 2H, 2′′′-3a-
H), 0.95 (t, J = 7.6 Hz, 3H, 3′′′-3b-H), 0.89 (t, J = 7.6 Hz, 3H, 3′′′-3a-
H) ppm; 13C NMR (100 MHz, CDCl3) δ 162.87 (CHO-3b), 162.48
(CHO-3a), 160.38 (C2-3b), 160.00 (C2-3a), 147.49 (C6-3a), 147.11
(C6-3b), 142.42 (C3′′-3a), 142.17 (C3′′-3b), 141.16 (C4-3a), 140.54
(C4-3b), 137.71 (C2′-3a), 135.68 (C2′-3b), 134.31 (C7′-3b), 134.06
(C7′-3a), 130.31 (C3′-3a), 130.00 (C5′-3a), 129.68 (C5′-3b), 129.31
(C5′′-3b), 129.24 (C3′-3b), 128.88 (C5′′-3a), 128.84 (C4′-3b),
128.53 (C6′-3a and -3b), 128.38 (C4′-3a), 109.90 (C4′′-3b), 109.67
(C4′′-3a), 108.26 (C3-3a and -3b), 98.30 (C5-3a), 97.89 (C5-3b),
51.98 (C1′′′-3b), 47.07 (C1′′′-3a), 22.49 (C2′′′-3b), 21.06 (C2′′′-
3a), 11.40 (C2′′′-3a), 11.07 (C3′′′-3b) ppm; HRMS (MALDI): m/z
calcd for C18H19Cl2N5OPd [M − Cl]+ 464.0310, found 464.0315. For
Palladium Complex 6e.
Purification by flash chromatography (DCM/MeOH = 10/1): a pale
yellow solid (136 mg, 54%), mp 219.6−220.3 °C; H NMR (400
1
MHz, DMSO-d6) δ 9.30 (d, J = 3.2 Hz, 1H, 5′′-H), 8.69 (t, J = 8.4 Hz,
1H, 5′-H), 8.49 (d, J = 8.8 Hz, 1H, 4-H), 8.46 (d, J = 2.4 Hz, 1H, 8′-
H), 8.24 (d, J = 7.6 Hz, 1H, 5-H), 8.15 (d, J = 2.0 Hz, 1H, 3-H), 8.09
(d, J = 7.2 Hz, 1H, 3′′-H), 7.72−7.65 (m, 2H, 6′-H and 7′-H), 7.03 (t,
J = 2.4 Hz, 1H, 4′′-H), 4.83 (t, J = 7.6 Hz, 2H, 1′′′-H), 1.94−1.85 (m,
2H, 2′′′-H), 0.97 (t, J = 7.2 Hz, 3H, 3′′′-H) ppm; 13C NMR (100
MHz, DMSO-d6) δ 162.80 (Pd−C), 149.34 (C2), 148.11 (C6),
147.18 (C4), 145.07 (C3′′), 133.98 (C4′), 133.11 (C9′), 129.91
(C6′), 127.49 (C5′′), 126.78 (C7′), 114.13 (C5′), 113.52 (C8′),
111.51 (C3), 110.69 (C5), 109.22 (C4′′), 49.17 (C1′′′), 23.44
(C2′′′), 11.08 (C3′′′) ppm; HRMS (MALDI): m/z calcd for
C18H17ClN6O3Pd [M − NO3]+ 446.0205, found 446.0226.
Palladium Complex 6h.
Purification by flash chromatography (DCM/MeOH = 10/1): a pale
1
yellow solid (134 mg, 45%), mp 208.9−209.6 °C; H NMR (400
Purification by flash chromatography (DCM/MeOH = 30/1): a pale
yellow solid (232 mg, 79%), mp 270.6−271.1 °C; H NMR (400
1
MHz, DMSO-d6) δ 9.23 (d, J = 2.8 Hz, 1H, 5′′-H), 8.65 (t, J = 7.6 Hz,
1H, 5′-H), 8.41 (t, J = 8.4 Hz, 2H, 4-H and 8′-H), 8.19 (d, J = 8.4 Hz,
1H, 5-H), 8.02 (d, J = 8.4 Hz, 2H, 3-H and 3′′-H), 7.69−7.62 (m, 2H,
6′-H and 7′-H), 6.98 (s, 1H, 4′′-H), 4.70 (t, J = 7.2 Hz, 2H, 1′′′-H),
1.87−1.76 (m, 2H, 2′′′-H), 0.92 (d, J = 7.2 Hz, 3H, 3′′′-H) ppm; 13C
NMR (100 MHz, DMSO-d6) δ 162.61 (Pd−C), 149.15 (C2), 147.95
(C6), 147.22 (C4), 144.94 (C3′′), 133.90 (C4′), 132.97 (C9′), 129.74
(C6′), 127.50 (C5′′), 126.81 (C7′), 114.04 (C5′), 113.44 (C8′),
111.51 (C3), 110.71 (C5), 109.24 (C4′′), 49.13 (C1′′′), 23.41
(C2′′′), 11.01 (C3′′′) ppm; 19F NMR (376 MHz, DMSO-d6) δ
−77.73 ppm; HRMS (MALDI): m/z calcd for C19H17ClF3N5O3PdS
[M − TfO]+ 446.0205, found 446.0214.
MHz, DMSO-d6) δ 9.27 (d, J = 3.2 Hz, 1H, 5′′-H), 8.68 (t, J = 8.4 Hz,
1H, 5′-H), 8.47 (d, J = 8.0 Hz, 1H, 4-H), 8.44 (d, J = 8.0 Hz, 1H, 8′-
H), 8.22 (d, J = 8.0 Hz, 1H, 5-H), 8.11 (s, 1H, 3-H), 8.06 (d, J = 8.8
Hz, 1H, 3′′-H), 7.72−7.65 (m, 2H, 6′-H and 7′-H), 7.02 (t, J = 2.4 Hz,
1H, 4′′-H), 4.77 (t, J = 7.2 Hz, 2H, 1′′′-H), 1.86 (hex, J = 8.0 Hz, 2H,
2′′′-H), 0.96 (t, J = 7.2 Hz, 3H, 3′′′-H) ppm; 13C NMR (100 MHz,
DMSO-d6) δ 162.73 (Pd−C), 149.28 (C2), 148.05 (C6), 147.18
(C4), 145.02 (C3′′), 133.94 (C4′), 133.05 (C9′), 129.85 (C6′),
127.48 (C5′′), 126.79 (C7′), 114.09 (C5′), 113.49 (C8′), 111.50
(C3), 110.68 (C5), 109.21 (C4′′), 49.14 (C1′′′), 23.43 (C2′′′), 11.05
(C3′′′) ppm; 19F NMR (376 MHz, DMSO-d6) δ −69.21, −71.10
H
Organometallics XXXX, XXX, XXX−XXX